The curious case of selenium hyperaccumulation in Coelospermum decipiens from the Cape York Peninsula (Queensland, Australia).

The tropical shrub Coelospermum decipiens (Rubiaceae) is an extreme selenium (Se) hyperaccumulator, reported to accumulate up to 1140 µg Se g-1 when found growing on soils with Se

Setting restorative goals with a regional outlook: Mine-rehabilitation outcomes influence landscape connectivity.

Mining is increasing worldwide and is typically associated with highly negative environmental impacts, such as habitat loss and fragmentation. To counteract these effects and improve restoration practices, decisions, such as setting mine rehabilitation goals, could incorporate the assessment and restoration of landscape connectivity into their regional and local-scale planning. The overarching goal of this work was to assess landscape connectivity for flora and fauna and explore mine-rehabilitation scenarios that can be used as a tool for prioritising biodiversity outcomes. Our study area comprised the Fitzroy Basin (Queensland, Australia), where the disturbance footprints from mining cover a cumulative area of 121,239 ha. We considered two scenarios: rehabilitation to agriculture and restoration to native ecosystems. To compare these scenarios, we created differential maps, which highlighted that restoring to native ecosystems represented connectivity gains over agricultural rehabilitation goals. These maps revealed three ways to prioritise rehabilitation outcomes, giving priority to mines that: 1) presented medium to high connectivity values, 2) covered a large area of influence (contributing to connectivity on a larger scale, regardless of current flow values), and 3) showed a gain of important paths/corridors. We explored four case studies and found that three benefited from restoration outcomes, while the fourth did not benefit by either scenario. Our methods can be used for decision-making in restoration ecology and conservation, including mine rehabilitation priorities and goals, as well as for evaluating connectivity gains or losses.

Reflectance spectroscopy as a promising tool for 'sensing' metals in hyperaccumulator plants.

MAIN CONCLUSION: The VNIR reflectance spectra of nickel hyperaccumulator plant leaves have spectral variations due to high nickel concentrations and this property could potentially be used for discovery of these plants.  Hyperaccumulator plants accumulate high concentrations of certain metals, including manganese, cobalt, or nickel. Of these metals, the divalent ions of nickel have three absorption bands in the visible to near-infrared region which may cause variations in the spectral reflectance of nickel hyperaccumulator plant leaves, but this has not been investigated previously. In this shortproof-of-concept study, the spectral reflectance of eight different nickel hyperaccumulator plant species leaves were subjected to visible and near-infrared and shortwave infrared (VNIR-SWIR) reflectance spectrum measurements in dehydrated state, and for one species, it was also assessed in hydrated state. Nickel concentrations in the plant leaves were determined with other methods and then correlated to the spectral reflectance data. Spectral variations centred at 1000 ± 150 nm were observed and had R-values varying from 0.46 to 0.96 with nickel concentrations. The extremely high nickel concentrations in nickel hyperaccumulator leaves reshape their spectral reflectance features, and the electronic transition of nickel-ions directly contributes to absorption at ~ 1000 nm. Given that spectral variations are correlated with nickel concentrations it make VNIR-SWIR reflectance spectrometry a potential promising technique for discovery of hyperaccumulator plants, not only in the laboratory or herbarium, but also in the field using drone-based platforms. This is a preliminary study which we hope will instigate further detailed research on this topic to validate the findings and to explore possible applications.

Anthropedogenesis in coal mine overburden; the need for a comprehensive, fundamental biogeochemical approach.

The primary solid waste product of surface coal mining is overburden (also known as spoil), the material that is moved to access the underlying coal seams. Once removed, this material is generally stored in large (>100 m in height) piles until it is re-contoured in preparation for post-mining rehabilitation, often remaining there for decades. Under ideal conditions, these new landforms would have at least 30 cm veneer of topsoil applied as a growth medium for plants. However, topsoil deficit conditions are common in coal mines, so the forced use of overburden that possess poor chemical, biological, and physical properties as the growth medium hinders plant establishment. To reach the characteristics of a functional soil that can support plants, it is necessary to dramatically improve spoil quality, i.e., accelerate pedogenesis, as an integral part of the rehabilitation process. For decades, overburden rehabilitation has often taken the traditional approach of using the agricultural practice of fertilizer application or focusing primarily on the types of plants used to stabilize these young landforms. In contrast, success improved when the rehabilitation procedures employed a more holistic approach to establishing self-sustaining plant-soil ecosystems. Here we identify constraints that impede spoil-to-soil transformation, discuss the global treatment options practiced post-mining for coal spoils, and describe how a comprehensive biogeochemical approach can be implemented in spoil reclamation processes going forward. Integrating the revitalization of soil organisms, reclamation of soil chemistry, soil structure, and landform into rehabilitation procedures can accelerate the transformation of coal spoils to functional soils. We believe that a shift in the nature of the question from "what chemicals and seeds should we add to coal spoil during site rehabilitation?" to something fundamentally more specific: "How do we induce pedogenic functions in coal spoils to develop fertile soils?" is needed.

Integrating microalgae production into mine closure plans.

Examples of successful mine closure and acceptable regional transitioning of mining areas are scarce. The recent changes to the environmental, social and governance (ESG) obligations of mining companies should help to ensure that water and land resources as well as post-mining employment opportunities are considered as a part of mine closure. Integrating microalgae production into mine closure plans is a potential opportunity for mining companies to improve many ESG outcomes. Mine sites with sufficient suitable land and water resources in high solar radiation geographies may be able to economically grow microalgae to capture atmospheric CO2, re-purpose saline mine waters, treat acidic and near-neutral pH metalliferous waters as well as produce soil ameliorants (biofertiliser, biostimulants and/or biochar) to improve mine rehabilitation outcomes. Microalgae production facilities may also provide an alternative industry and employment opportunities to help transition regional mining towns that have become reliant on mining activities. The potential economic, environmental and social benefits of using mine-influenced water for microalgae production may offer an opportunity to successfully close and transition some mining landscapes.

X-ray fluorescence spectroscopy (XRF) for metallome analysis of herbarium specimens.

BACKGROUND: "Herbarium X-ray Fluorescence (XRF) Ionomics" is a new quantitative approach for extracting the elemental concentrations from herbarium specimens using handheld XRF devices. These instruments are principally designed for dense sample material of infinite thickness (such as rock or soil powder), and their built-in algorithms and factory calibrations perform poorly on the thin dry plant leaves encountered in herbaria. While empirical calibrations have been used for 'correcting' measured XRF values post hoc, this approach has major shortcomings. As such, a universal independent data analysis pipeline permitting full control and transparency throughout the quantification process is highly desirable. Here we have developed such a pipeline based on Dynamic Analysis as implemented in the GeoPIXE package, employing a Fundamental Parameters approach requiring only a description of the measurement hardware and derivation of the sample areal density, based on a universal standard. RESULTS: The new pipeline was tested on potassium, calcium, manganese, iron, cobalt, nickel, and zinc concentrations in dry plant leaves. The Dynamic Analysis method can correct for complex X-ray interactions and performs better than both the built-in instrument algorithms and the empirical calibration approach. The new pipeline is also able to identify and quantify elements that are not detected and reported by the device built-in algorithms and provides good estimates of elemental concentrations where empirical calibrations are not straightforward. CONCLUSIONS: The new pipeline for processing XRF data of herbarium specimens has a greater accuracy and is more robust than the device built-in algorithms and empirical calibrations. It also gives access to all elements detected in the XRF spectrum. The new analysis pipeline has made Herbarium XRF approach even more powerful to study the metallome of existing plant collections.

Micro-analytical and molecular approaches for understanding the distribution, biochemistry, and molecular biology of selenium in (hyperaccumulator) plants.

MAIN CONCLUSION: Micro-analytical techniques to untangle Se distribution and chemical speciation in plants coupled with molecular biology analysis enable the deciphering of metabolic pathways responsible for Se tolerance and accumulation. Selenium (Se) is not essential for plants and is toxic at high concentrations. However, Se hyperaccumulator plants have evolved strategies to both tolerate and accumulate > 1000 µg Se g-1 DW in their living above-ground tissues. Given the complexity of the biochemistry of Se, various approaches have been adopted to study Se metabolism in plants. These include X-ray-based techniques for assessing distribution and chemical speciation of Se, and molecular biology techniques to identify genes implicated in Se uptake, transport, and assimilation. This review presents these techniques, synthesises the current state of knowledge on Se metabolism in plants, and highlights future directions for research into Se (hyper)accumulation and tolerance. We conclude that powerful insights may be gained from coupling information on the distribution and chemical speciation of Se to genome-scale studies to identify gene functions and molecular mechanisms that underpin Se tolerance and accumulation in these ecologically and biotechnologically important plants species. The study of Se metabolism is challenging and is a useful testbed for developing novel analytical approaches that are potentially more widely applicable to the study of the regulation of a wide range of metal(loid)s in hyperaccumulator plants.

Cellular-level distribution of manganese in Macadamia integrifolia, M. ternifolia, and M. tetraphylla from Australia.

Macadamia integrifolia and M. tetraphylla, unlike M. ternifolia, are known for their edible nuts. All three species over-accumulate the trace metal nutrient manganese (Mn) in their shoots. This study seeks to examine tissue- and cellular-level distribution of Mn and other plant nutrients in the three Macadamia species. The distribution of Mn, calcium, iron, and potassium were investigated in whole leaves and cross-sections of roots, petioles, and leaves using synchrotron-based X-ray fluorescence microscopy (XFM) in M. integrifolia, M. tetraphylla, and M. ternifolia. The results show Mn sequestration primarily in the leaf and midrib palisade mesophyll cells of all three species. Leaf interveinal regions, root cortical cells, and phloem cells were also found to be Mn loaded. The current study confirms earlier findings but further reveals that Mn is concentrated in the vacuoles of mesophyll cells owing to the exceptional resolution of the synchrotron XFM data, and the fact that fresh hydrated samples were used. New insights gained here into Mn compartmentalization in these highly Mn-tolerant Macadamias expand knowledge about potentially toxic over-accumulation of an essential micronutrient, which ultimately stands to inform strategies around farming edible species in particular.

Farming for battery metals.

Globally, there is a major shift to electric vehicles to combat climate change and these vehicles are currently powered by lithium-ion batteries that contain nickel cobalt manganese oxide materials. This technological change from internal combustion engines means that demand for battery minerals will need to increase by factors of >20 for the critical metals required for batteries in the next three decades. If this scenario plays out, it will require a dramatic increase in the worldwide capacity to produce nickel, manganese, cobalt, and lithium raw materials of sufficient purity. This demand could partly be met by agromining technology, which is a 'green technology' that extracts valuable products, including high-purity metal salts useful for the battery industry, from selected plants known as 'metal crops'. Farming for nickel, cobalt, and manganese is currently within reach, whereas lithium agromining has not yet been developed but has potential. SYNOPSIS: Agromining offers a sustainable approach to economically produce battery-grade raw materials from unconventional sources, thus, producing 'green technologies' from 'green sources'.

The X-ray structure of juvenile hormone diol kinase from the silkworm Bombyx mori.

Insect juvenile hormones (JHs) are a family of sesquiterpenoid molecules that are secreted into the haemolymph. JHs have multiple roles in insect development, metamorphosis and sexual maturation. A number of pesticides work by chemically mimicking JHs, thus preventing insects from developing and reproducing normally. The haemolymph levels of JH are governed by the rates of its biosynthesis and degradation. One enzyme involved in JH catabolism is JH diol kinase (JHDK), which uses ATP (or GTP) to phosphorylate JH diol to JH diol phosphate, which can be excreted. The X-ray structure of JHDK from the silkworm Bombyx mori has been determined at a resolution of 2.0 Šwith an R factor of 19.0% and an Rfree of 24.8%. The structure possesses three EF-hand motifs which are occupied by calcium ions. This is in contrast to the recently reported structure of the JHDK-like-2 protein from B. mori (PDB entry 6kth), which possessed only one calcium ion. Since JHDK is known to be inhibited by calcium ions, it is likely that our structure represents the calcium-inhibited form of the enzyme. The electrostatic surface of the protein suggests a binding site for the triphosphate of ATP close to the N-terminal end of the molecule in a cavity between the N- and C-terminal domains. Superposition with a number of calcium-activated photoproteins suggests that there may be parallels between the binding of JH diol to JHDK and the binding of luciferin to aequorin.

The X-ray structure of L-threonine dehydrogenase from the common hospital pathogen Clostridium difficile.

In many prokaryotes, the first step of threonine metabolism is catalysed by the enzyme threonine dehydrogenase (TDH), which uses NAD+ to oxidize its substrate to 2-amino-3-ketobutyrate. The absence of a functional TDH gene in humans suggests that inhibitors of this enzyme may have therapeutic potential against pathogens which are reliant on this enzyme. Here, TDH from Clostridium difficile has been cloned and overexpressed, and the X-ray structure of the apoenzyme form has been determined at 2.6 Šresolution.

Indigenous forest livelihoods and bauxite mining: A case-study from northern Australia.

Bauxite mining operations are increasingly sited on Indigenous-owned land, particularly in tropical areas, including northern Australia. The environmental impacts of bauxite mining are significant. Native vegetation, including commercially valuable forests, is cleared and typically windrowed and burnt. For many Indigenous Australians, mining of their land creates much concern about biocultural, community health and livelihood impacts from the loss of access to traditional lands and resources, and the ability to 'care for country'. Improved pre-mining utilisation of forest resources and effective mine rehabilitation can mitigate some of these impacts and it is important to Indigenous communities that they are engaged in these processes. But Indigenous peoples' expectations are rarely considered or adequately addressed in site clearing activities or mine completion criteria, and there is limited guidance on how their expected outcomes can be monitored and evaluated for mine closure and relinquishment. This paper reports on a case-study of the Western Cape York Peninsula bauxite mining region in northern Australia. The paper reviews mine rehabilitation in the case-study region, including related Indigenous forest livelihoods initiatives, presents local Indigenous peoples' expectations for pre- and post-mining forest and landscape management as an integrated mining-community forestry 'vision', and discusses implications for mine completion criteria, mine closure and relinquishment. The findings highlight the need for Indigenous peoples' full and transparent free, prior and informed consent participation in all aspects of mine closure planning, and for further research to trial the development and assessment of mine completion criteria linked to local biocultural landscape restoration and Indigenous livelihoods. The findings can inform mining policymakers, regulators and industry professionals on the design, implementation and monitoring of mine completion criteria and associated pre- and post-mining management that will improve environmental outcomes and socio-cultural benefits for Indigenous communities impacted by mining.

Intensive cycling of nickel in a New Caledonian forest dominated by hyperaccumulator trees.

The hyperaccumulator Pycnandra acuminata is a New Caledonian rainforest tree known to have the highest concentration of nickel in any living organism, with 25 wt% nickel in its latex. All trees (with a diameter of >10 cm) and soil profiles in a 0.25-hectare permanent plot were sampled to assess the biogeochemical compartmentalisation of nickel in a dense stand of P. acuminata trees. Nickel stable isotope analysis permitted insights into the cycling of nickel in this ecosystem. The total tree biomass of the plot was calculated to be 281 tonnes ha-1 , which contained 0.44 kg of cobalt, 49.1 kg of manganese, 257 kg of nickel and 6.76 kg of zinc. Nickel stable isotope analysis identified the biotic origin of the nickel in the soil upper layers, with P. acuminata shoots enriched in lighter nickel isotopes. The δ60 Ni latex signature suggests that long-distance transport, radial xylem and phloem loading are at play in P. acuminata.

Incidence of hyperaccumulation and tissue-level distribution of manganese, cobalt, and zinc in the genus Gossia (Myrtaceae).

The rare phenomenon of plant manganese (Mn) hyperaccumulation within the Australian flora has previously been detected in the field, which suggested that the tree genus Gossia (Myrtaceae) might contain new Mn hyperaccumulators. We conducted the first growth experiment on Gossia using a multi-factorial dosing trial to assess Mn, cobalt (Co), and zinc (Zn) (hyper)accumulation patterns in selected Gossia species (G. fragrantissima and G. punctata) after a systematic assessment of elemental profiles on all holdings of the genus Gossia at the Queensland Herbarium using handheld X-ray fluorescence spectroscopy. We then conducted detailed in situ analyses of the elemental distribution of Mn, Co, Zn and other elements at the macro (organ) and micro (cellular) levels with laboratory- and synchrotron-based X-ray fluorescence microscopy (XFM). Gossia pubiflora and Gossia hillii were newly discovered to be Mn hyperaccumulator plants. In the dosing trial, G. fragrantissima accumulated 17 400 µg g-1 Mn, 545 µg g-1 Co, and 13 000 µg g-1 Zn, without signs of toxicity. The laboratory-based XFM revealed distinct patterns of accumulation of Co, Mn, and Zn in G. fragrantissima, while the synchrotron XFM showed their localization in foliar epidermal cells, and in the cortex and phloem cells of roots. This study combined novel analytical approaches with controlled experimentation to examine metal hyperaccumulation in slow-growing tropical woody species, thereby enabling insight into the phenomenon not possible through field studies.

Treasure from trash: Mining critical metals from waste and unconventional sources.

To meet future technological demands of our growing global community new sources of industry critical metals need to be identified. To meet these demands, extracting minerals from larger, lower grade deposits across most commodities is required, which in turn generates ever increasing amounts of mine wastes. We propose that agromining could be used to enables access to unconventional resources not viable using existing minerals processing techniques. This innovative technique relies on so-called hyperaccumulator plants to bio-concentrate high levels of metals into living biomass which can then be extracted from the harvested bio-ore. Producing critical metals, such as nickel, cobalt and thallium, efficiently and sustainably using agromining appears to be well within reach, but this technology needs industrial champions to develop demonstration sites that are scaled appropiately in areas where it is feasible.

Novel Insights Into the Hyperaccumulation Syndrome in Pycnandra (Sapotaceae).

The discovery of nickel hyperaccumulation, in Pycnandra acuminata, was the start of a global quest in this fascinating phenomenon. Despite recent advances in the physiology and molecular genetics of hyperaccumulation, the mechanisms and tolerance of Ni accumulation in the most extreme example reported to date, P. acuminata, remains enigmatic. We conducted a hydroponic experiment to establish Ni tolerance levels and translocation patterns in roots and shoots of P. acuminata, and analyzed elemental partitioning to gain insights into Ni regulation. We combined a phylogeny and foliar Ni concentrations to assess the incidence of hyperaccumulation within the genus Pycnandra. Hydroponic dosing experiments revealed that P. acuminata can resist extreme Ni concentrations in solution (up to 3,000 µM), and dosing at 100 µM Ni was beneficial to growth. All plant parts were highly enriched in Ni, but the latex had extreme Ni concentrations (124,000 µg g-1). Hyperaccumulation evolved independently in only two subgenera and five species of the genus Pycnandra. The extremely high level of Ni tolerance is posited to derive from the unique properties of laticifers. The evolutionary and ecological significance of Ni hyperaccumulation in Pycnandra is discussed in light of these findings. We suggest that Ni-rich laticifers might be more widespread in the plant kingdom and that more investigation is warranted.

Nickel hyperaccumulation in New Caledonian Hybanthus (Violaceae) and occurrence of nickel-rich phloem in Hybanthus austrocaledonicus.

BACKGROUND AND AIMS: Hybanthus austrocaledonicus (Violaceae) is a nickel (Ni) hyperaccumulator endemic to New Caledonia. One of the specimens stored at the local herbarium had a strip of bark with a remarkably green phloem tissue attached to the sheet containing over 4 wt% Ni. This study aimed to collect field samples from the original H. austrocaledonicus locality to confirm the nature of the green 'nickel-rich phloem' in this taxon and to systematically assess the occurrence of Ni hyperaccumulation in H. austrocaledonicus and Hybanthus caledonicus populations. METHODS: X-ray fluorescence spectroscopy scanning of all collections of the genus Hybanthus (236 specimens) was undertaken at the Herbarium of New Caledonia to reveal incidences of Ni accumulation in populations of H. austrocaledonicus and H. caledonicus. In parallel, micro-analytical investigations were performed via synchrotron X-ray fluorescence microscopy (XFM) and scanning electron microscopy with X-ray microanalysis (SEM-EDS). KEY RESULTS: The extensive scanning demonstrated that Ni hyperaccumulation is not a characteristic common to all populations in the endemic Hybanthus species. Synchrotron XFM revealed that Ni was exclusively concentrated in the epidermal cells of the leaf blade and petiole, conforming with the majority of (tropical) Ni hyperaccumulator plants studied to date. SEM-EDS of freeze-dried and frozen-hydrated samples revealed the presence of dense solid deposits in the phloem bundles that contained >8 wt% nickel. CONCLUSIONS: The occurrence of extremely Ni-rich green phloem tissues appears to be a characteristic feature of tropical Ni hyperaccumulator plants.

Frequency distribution of foliar nickel is bimodal in the ultramafic flora of Kinabalu Park (Sabah, Malaysia).

BACKGROUND AND AIMS: The aim of this study was to test the frequency distributions of foliar elements from a large dataset from Kinabalu Park (Sabah, Malaysia) for departure from unimodality, indicative of a distinct ecophysiological response associated with hyperaccumulation. METHODS: We collected foliar samples (n = 1533) comprising 90 families, 198 genera and 495 plant species from ultramafic soils, further foliar samples (n = 177) comprising 45 families, 80 genera and 120 species from non-ultramafic soils and corresponding soil samples (n = 393 from ultramafic soils and n = 66 from non-ultramafic soils) from Kinabalu Park (Sabah, Malaysia). The data were geographically (Kinabalu Park) and edaphically (ultramafic soils) constrained. The inclusion of a relatively high proportion (approx. 14 %) of samples from hyperaccumulator species [with foliar concentrations of aluminium and nickel (Ni) >1000 µg g-1, cobalt, copper, chromium and zinc >300 µg g-1 or manganese (Mn) >10 mg g-1] allowed for hypothesis testing. KEY RESULTS: Frequency distribution graphs for most elements [calcium (Ca), magnesium (Mg) and phosphorus (P)] were unimodal, although some were skewed left (Mg and Mn). The Ni frequency distribution was bimodal and the separation point for the two modes was between 250 and 850 µg g-1. CONCLUSIONS: Accounting for statistical probability, the established empirical threshold value (>1000 µg g-1) remains appropriate. The two discrete modes for Ni indicate ecophysiologically distinct behaviour in plants growing in similar soils. This response is in contrast to Mn, which forms the tail of a continuous (approximately log-normal) distribution, suggestive of an extension of normal physiological processes.

Elemental distribution and chemical speciation of copper and cobalt in three metallophytes from the copper-cobalt belt in Northern Zambia.

Three metallophyte species, Persicaria capitata, P. puncata (Polygonaceae), Conyza cordata (Asteraceae) from mineral wastes in the Zambian copper-cobalt belt were studied. This study focused on the elemental distribution in the roots, stems and leaves, using a range of techniques: micro-PIXE, SEM-EDS synchrotron XFM and XAS. The species differed in their responses to growing on Co-Cu-enriched soils: Persicaria puncata is a Co hyperaccumulator (up to 1060 µg g-1 in leaves), while Persicaria capitata and Conyza cordata are Co-excluders. All three species are Cu-accumulators. The highest concentrations of Cu-Co are in the epidermal cells, whereas in Persicaria puncata Co was also enriched in the phloem. The Co coordination chemistry shows that an aqueous Co(ii)-tartrate complex was the predominant component identified in all plants and tissues, along with a minor component of a Co(iii) compound with oxygen donor ligands. For Cu, there was considerable variation in the Cu speciation in the various tissues and across the three species. In contrast to hyperaccumulator plants, excluder and accumulator type plants have received far less attention. This study highlights the different biopathways of transition elements (Cu, Co) in hyper-tolerant plant species showing different responses to metalliferous environments.